EP0396243A1 - The inhibition of corrosion in aqueous systems - Google Patents

The inhibition of corrosion in aqueous systems Download PDF

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Publication number
EP0396243A1
EP0396243A1 EP90303075A EP90303075A EP0396243A1 EP 0396243 A1 EP0396243 A1 EP 0396243A1 EP 90303075 A EP90303075 A EP 90303075A EP 90303075 A EP90303075 A EP 90303075A EP 0396243 A1 EP0396243 A1 EP 0396243A1
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Prior art keywords
phosphonate
formula
polymer
ppm
polyampholyte
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German (de)
French (fr)
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Brian Greaves
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WR Grace and Co Conn
WR Grace and Co
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WR Grace and Co Conn
WR Grace and Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • the present invention relates to inhibiting and/or preventing corrosion of iron based metals which are in contact with aqueous systems, such as cooling water systems.
  • Iron and iron metal containing alloys such as mild steel are well-known materials used in constructing the apparatus of aqueous systems in which system water circulates, contacts the iron based metal surface, and may be concentrated, such as by evaporation of a portion of the water from the system.
  • Chromates and inorganic polyphosphates have been used in the past to inhibit the corrosion of metals which is experienced when the metals are brought into contact with water.
  • the chromates though effective, are highly toxic and, consequently, present handling and disposal problems.
  • the polyphosphates are relatively non-toxic, but tend to hydrolyze to form orthophosphate which in turn can create scale and sludge problems in aqueous systems.
  • excess phosphate compounds can provide disposal problems as nutrient sources. Borates, nitrates, and nitrites have also been used for corrosion inhibition. These too can serve as nutrients in low concentrations, but represent potential health concerns at high concentrations.
  • organic corrosion inhibitors which can reduce reliance on the traditional inorganic inhibitors.
  • organic inhibitors successfully employed are numerous organic phosphonates. These compounds may generally be used without detrimental interference from other conventional water treatment additives but do not always give optional performance when used alone. However there is a general desire to reduce the amount of material which is needed, both on grounds of cost and for environmental reasons.
  • a method for controlling corrosion in an aqueous svstem which comprises incorporating in the system at least one phosphonate of the formula: in which R1 represents hydrogen or a C1-C4 alkyl group and R represents -COOH or -PO3H2 or a salt thereof, and at least one polyampholyte which possesses recurring units of the formula and either recurring units of the formula: or recurring units of the formula in which R1 represents hydrogen or a C1-C4 alkyl group, X represents hydrogen or -COOH, Y represents in which Z represents -O- or -NH-, n is 2 or 3 and R2, R3, R4 and R5 individually represent C1-C4 alkyl, especially methyl or ethyl and A represents an anion especially Cl, Br, CH3SO4 or C2H5SO4 or a salt thereof.
  • the copolymers are preferably derived from acrylic acid, methacrylic acid or maleic acid as the first component.
  • the quaternary ammonium components are preferably those in which Y represents
  • the molar ratio of the two component units is preferably from 1:4 to 4:1. In general the molar amount of quaternary units should not significantly exceed the molar amount of the acid units. The preferred ratio is about 1:1.
  • copolymers used in the present invention can also contain recurring units from other monomers provided these are non ionic.
  • specific examples of such monomers include acrylamide, C1-C4 alkyl or hydroxyalkyl, e.g. hydroxypropyl, acrylate and methacrylate esters.
  • the molecular weight of the copolymers used corresponds to an intrinsic viscosity measured in molar aqueous sodium chloride solution, of from 0.05 to 2.5 dl/gm.
  • the phosphonates and polymers can be used in the form of salts, typically alkali metal, e.g. sodium or potassium, or amine, e.g. triethanolamine, diethanolamine or monoethanolamine, salts.
  • the present invention also provides a composition suitable for addition to an aqueous system which comprises at least one phosphonate of formula (I) as defined above together with a polyampholyte possessing recurring units of formula (II) and of formula (III) or (IV). Normally the composition will be in the form of an aqueous solution.
  • the relative proportions of phosphonate and copolymer will depend to some extent on the nature of the units forming the copolymer and the relative proportions of those units in the copolymer. In general, though, the molar ratio will be from 20:1 to 1:20 and, more particularly, from 10:1 to 1:10. Usually it will be desirable for the phosphonate to be present in a larger quantity than that of the polyampholyte. Typically the composition will contain from 1 to 10%, preferably 1.5 to 5%, especially 1.5 to 3%, by weight of polymer and 2 to 25%, preferably 5 to 20%, especially 5 to 15%, by weight of phosphonate.
  • the phosphonate will be added to the system in an amount from 1 to 100, preferably 5 to 30 and especially 10 to 30, ppm while the corresponding amounts for the polymer will be 0.1 to 150 ppm, 0.5 to 50 ppm and 1 to 40 ppm, respectively.
  • compositions of this invention may include other ingredients customarily employed in water treatment including lignin derivatives, other polymers, tannins, other phosphonates, biocides and yellow metal corrosion inhibitors especially benzothiazole and tolyltriazole, phosphates, zinc salts and molybdates.
  • pH of the composition can be adjusted, if desired, preferably to about 7-7.5 by the inclusion of, say, alkalis such as potassium hydroxide and amines such as triethanolamine.
  • Specific preferred formulations include the following: (i) Copolymer of methacrylic acid and diallyl-dimethyl ammonium chloride; mole ratio 1:1 2.0% (Active material) Hydroxyphosphonoacetic acid 10.0% Copolymer of methyacrylic acid/acrylamide 2.5% Benzotriazole 1.0% Potassium Hydroxide (50% solution) 10.0% Triethanolamine 15.0% Soft Water to 100% (pH 7.0 - 7.5) % given on a weight/weight basis (ii) Polymer of methacrylic acid and diallyl-dimethyl ammonium chloride; mole ratio 1:1 2.0% Hydroxyphosphono acetic acid 10.0% Benzotriazole 1.5% Soft Water to (formulation in the acid form) 100.0%
  • Tests were carried out using a laboratory scale simulated open recirculating cooling svstem, under the following conditions: System Water : 150 ppm Ca hardness 150 ppm M Alkalinity Water Temperature : 54°C pH : 8.6 Flow rate past test coupons : 2 ft/sec (Line) 0.2 ft/sec (Pond) Passivation Dose : 3 x maintenance dose for a period of 1 day Duration of Test : 3 days

Abstract

A method for controlling corrosion in an aqueous system which comprises incorporating in the system at least one phosphonate of the formula:
Figure imga0001
 in which R₁ represents hydrogen or a C₁-C₄ alkyl group and R₂ represents -COOH or -PO₃H₂ or a salt thereof, and at least one polyampholyte which possesses recurring units of the formula
Figure imga0002
 and either recurring units of the formula:
Figure imga0003
 or recurring units of the formula
Figure imga0004
 in which R₁ represents hydrogen or a C₁-C₄ alkyl group, X represents hydrogen or -COOH, Y represents in which Z represents -O- or -NH-, n is 2 or 3 and R₂, R₃, R₄ and R₅ individually represent C₁-C₄ alkyl, especially methyl or ethyl, and A represents an anion especially Cl, Br, CH₃SO₄ or C₂H₅SO₄, or a salt thereof.

Description

  • The present invention relates to inhibiting and/or preventing corrosion of iron based metals which are in contact with aqueous systems, such as cooling water systems.
  • Iron and iron metal containing alloys such as mild steel are well-known materials used in constructing the apparatus of aqueous systems in which system water circulates, contacts the iron based metal surface, and may be concentrated, such as by evaporation of a portion of the water from the system.
  • It is known that various materials which are naturally or synthetically occurring in the aqueous systems, especially systems using water derived from natural resources such as seawater, rivers, lakes and the like, attack iron-based or ferrous metals. Typical devices in which the iron metal parts are subject to corrosion include evaporators, single and multi-pass heat exchangers, cooling towers, and associated equipment and the like. As the system water passes through or over the device, a portion of the system water evaporates causing a concentration of the dissolved materials such as chloride and sulphate ions contained in the water. These materials approach and reach a concentration at which they may cause severe pitting and corrosion which eventually requires replacement of the metal parts. Various corrosion inhibitors have been used previously.
  • Chromates and inorganic polyphosphates have been used in the past to inhibit the corrosion of metals which is experienced when the metals are brought into contact with water. The chromates, though effective, are highly toxic and, consequently, present handling and disposal problems. The polyphosphates are relatively non-toxic, but tend to hydrolyze to form orthophosphate which in turn can create scale and sludge problems in aqueous systems. Moreover, where there is a concern over eutrophication of receiving waters, excess phosphate compounds can provide disposal problems as nutrient sources. Borates, nitrates, and nitrites have also been used for corrosion inhibition. These too can serve as nutrients in low concentrations, but represent potential health concerns at high concentrations.
  • Much recent research has concerned the development of organic corrosion inhibitors which can reduce reliance on the traditional inorganic inhibitors. Among the organic inhibitors successfully employed are numerous organic phosphonates. These compounds may generally be used without detrimental interference from other conventional water treatment additives but do not always give optional performance when used alone. However there is a general desire to reduce the amount of material which is needed, both on grounds of cost and for environmental reasons.
  • It has now been found that the use of a combination of particular polyampholytes and particular phosphonates gives rise to a synergistic mixture in the control of corrosion of ferrous metals in contact with aqueous systems, in particular cooling water systems. In other words the effectiveness of certain phosphonates can be enhanced significantly by using them together with certain polyampholytes. The use of even low concentrations of these polyampholytes in combination with the phosphonates gives rise to outstandingly low corrosion rates.
  • According to the present invention there is provided a method for controlling corrosion in an aqueous svstem which comprises incorporating in the system at least one phosphonate of the formula:
    Figure imgb0001
     in which R₁ represents hydrogen or a C₁-C₄ alkyl group and R represents -COOH or -PO₃H₂ or a salt thereof, and at least one polyampholyte which possesses recurring units of the formula
    Figure imgb0002
     and either recurring units of the formula:
    Figure imgb0003
     or recurring units of the formula
    Figure imgb0004
     in which R₁ represents hydrogen or a C₁-C₄ alkyl group, X represents hydrogen or -COOH, Y represents
    Figure imgb0005
     in which Z represents -O- or -NH-, n is 2 or 3 and R₂, R₃, R₄ and R₅ individually represent C₁-C₄ alkyl, especially methyl or ethyl and A represents an anion especially Cl, Br, CH₃SO₄ or C₂H₅SO₄ or a salt thereof.
  • Preferred phosphonates for use in the present invention include hydroxyphosphono acetic acid (R₁ = H; R₂ = COOH) and hydroxy ethylidene diphosphonic acid (R₁ = CH₃; R₂ = PO₃H₂).
  • The copolymers are preferably derived from acrylic acid, methacrylic acid or maleic acid as the first component. The quaternary ammonium components are preferably those in which Y represents
    Figure imgb0006
  • The molar ratio of the two component units is preferably from 1:4 to 4:1. In general the molar amount of quaternary units should not significantly exceed the molar amount of the acid units. The preferred ratio is about 1:1.
  • The copolymers used in the present invention can also contain recurring units from other monomers provided these are non ionic. Specific examples of such monomers include acrylamide, C₁-C₄ alkyl or hydroxyalkyl, e.g. hydroxypropyl, acrylate and methacrylate esters.
  • In general the molecular weight of the copolymers used corresponds to an intrinsic viscosity measured in molar aqueous sodium chloride solution, of from 0.05 to 2.5 dl/gm. As indicated the phosphonates and polymers can be used in the form of salts, typically alkali metal, e.g. sodium or potassium, or amine, e.g. triethanolamine, diethanolamine or monoethanolamine, salts.
  • While it is possible to add the phosphonate and polyampholyte separately to the aqueous system it will generally be more convenient to add them together in the form of a composition. Accordingly, the present invention also provides a composition suitable for addition to an aqueous system which comprises at least one phosphonate of formula (I) as defined above together with a polyampholyte possessing recurring units of formula (II) and of formula (III) or (IV). Normally the composition will be in the form of an aqueous solution.
  • The relative proportions of phosphonate and copolymer will depend to some extent on the nature of the units forming the copolymer and the relative proportions of those units in the copolymer. In general, though, the molar ratio will be from 20:1 to 1:20 and, more particularly, from 10:1 to 1:10. Usually it will be desirable for the phosphonate to be present in a larger quantity than that of the polyampholyte. Typically the composition will contain from 1 to 10%, preferably 1.5 to 5%, especially 1.5 to 3%, by weight of polymer and 2 to 25%, preferably 5 to 20%, especially 5 to 15%, by weight of phosphonate.
  • In general the phosphonate will be added to the system in an amount from 1 to 100, preferably 5 to 30 and especially 10 to 30, ppm while the corresponding amounts for the polymer will be 0.1 to 150 ppm, 0.5 to 50 ppm and 1 to 40 ppm, respectively.
  • The compositions of this invention may include other ingredients customarily employed in water treatment including lignin derivatives, other polymers, tannins, other phosphonates, biocides and yellow metal corrosion inhibitors especially benzothiazole and tolyltriazole, phosphates, zinc salts and molybdates. In addition the pH of the composition can be adjusted, if desired, preferably to about 7-7.5 by the inclusion of, say, alkalis such as potassium hydroxide and amines such as triethanolamine.
  • Specific preferred formulations include the following:
    (i) Copolymer of methacrylic acid and diallyl-dimethyl ammonium chloride; mole ratio 1:1 2.0% (Active material)
    Hydroxyphosphonoacetic acid 10.0%
    Copolymer of methyacrylic acid/acrylamide 2.5%
    Benzotriazole 1.0%
    Potassium Hydroxide (50% solution) 10.0%
    Triethanolamine 15.0%
    Soft Water to 100% (pH 7.0 - 7.5) % given on a weight/weight basis
    (ii) Polymer of methacrylic acid and diallyl-dimethyl ammonium chloride; mole ratio 1:1 2.0%
    Hydroxyphosphono acetic acid 10.0%
    Benzotriazole 1.5%
    Soft Water to (formulation in the acid form) 100.0%
  • The following Examples further illustrate the present invention.
    • Examples
  • Tests were carried out using a laboratory scale simulated open recirculating cooling svstem, under the following conditions:
    System Water :
    150 ppm Ca hardness
    150 ppm M Alkalinity
    Water Temperature : 54°C
    pH : 8.6
    Flow rate past test coupons : 2 ft/sec (Line) 0.2 ft/sec (Pond)
    Passivation Dose : 3 x maintenance dose for a period of 1 day
    Duration of Test : 3 days
  • The following results were obtained:
    Corrosion Rate mpy
    Test No Additive Dose/ppm Mild Steel (Line) Mild Steel (Pond)
    No treatment - 40.5 48.0
    1 Phosphonate 1 10/- 14.1 10.5
    2 Phosphonate 1/Polymer 1 10/1 4.2 5.3
    3 Phosphonate 1/Polymer 1 10/2 1.6 1.0
    4 Phosphonate 1/Polymer 1 10/2.5 2.4 2.3
    5 Phosphonate 1/Polymer 1 10/4 8.0 15.2
    6 Phosphonate 1/Polymer 1 10/6 12.2 14.0
    8 Polymer 1 -/10 25.6 26.4
    9 Phosphonate 1/Polymer 2 10/2.5 32.6 27.1
    10 Phosphonate 1/Polymer 3 10/2.5 2.2 9.9
    11 Phosphonate 1/Polymer 5 10/2 1.8 1.0
    12 Phosphonate 1/Polymer 6 10/2 3.7 4.9
    13 Phosphonate 1/Polymer 4 10/2.5 9.6 7.9
    14 Phosphonate 1/Polymer 4 10/5.0 6.8 5.7
    15 Phosphonate 1/Polymer 4 10/10 3.7 3.8
    16 Phosphonate 1/Polymer 4 10/12.5 4.9 5.0
    17 Phosphonate 1/Polymer 4 -/10 27.1 27.4
    18 Phosphonate 2/Polymer 4 10/10 30.7 24.8
    19 Phosphonate 3/Polymer 1 10/2 8.4 7.7
    20 Phosphonate 3/ - 10/- 24.3 25.8
    • Phosphonate 1 = Hydroxyphosphonoacetic acid
    • Phosphonate 2 = Nitrilotrismethylenephosphonic acid
    • Phosphonate 3 = Hydroxyethylidene diphosphonic acid
    • Phosphonate 4 = 2-phosphonobutane-1,2,4-tricarboxylic acid
    • Polymer 1 - Copolymer of methacrylic cid and diallyl-dimethyl ammonium chloride (DADMAC). Mole ratio 1:1.
    • Polymer 2 = Copolymer of methacrylic acid and DADMAC. Mole ratio 1:4.
    • Polymer 3 = Copolymer of methacrylic acid and DADMAC ammonium chloride. Mole ratio 4:1
    • Polymer 4 = Copolymer of methacrylic acid and methacryloyloxyethyltrimethylammonium methosulphate in mole ratio 1:1.
    • Polymer 5 = Copolymer of Acrylic acid/DADMAC in mole ratio 1:1
    • Polymer 6 = Copolymer of maleic acid/DADMAC in mole ratio 1:1.
  • The following tests were carried out in a different water:-
    System water :
    50 ppm Ca hardness
    50 ppm M Alkalinity
    Corrosion Rate mpy
    Test No Additive Dose/ppm Mild Steel (Line) Mild Steel (Pond)
    21 Phosphonate 1/Polymer 1 10/10 1.7 1.5
    22 Phosphonate 1/Polymer 5 10/10 2.0 1.9
    23 Phosphonate 2/- 10 26.8 27.5
    24 Phosphonate 4/Polymer 1 10/2 24.6 26.3
  • These results for the combination used in the present invention (21 and 22) are excellent for an all organic corrosion inhibitor being used in a very corrosive water. The synergistic effect will be noted and contrasted with the results of other phosphonates (2 and 4).

Claims (20)

1. A method for controlling corrosion in an aqueous system which comprises incorporating in the system at least one phosphonate of the formula:
Figure imgb0013
 in which R₁ represents hydrogen or a C₁-C₄ alkyl group and R₂ represents -COOH or -PO₃H₂ or a salt thereof, and at least one polyampholyte which possesses recurring units of the formula
Figure imgb0014
 and either recurring units of the formula:
Figure imgb0015
 or recurring units of the formula
Figure imgb0016
 in which R₁ represents hydrogen or a C₁-C₄ alkyl group, X represents hydrogen or -COOH, Y represents
Figure imgb0017
 in which Z represents -O- or -NH- and R₂, R₃, R₄ and R₅ individually represent C₁-C₄ alkyl, especially methyl or ethyl, and A represents an anion especially Cl, Br, CH₃SO₄ or C₂H₅SO₄, or a salt thereof.
2. A method according to claim 1 in which R₁ represents hydrogen or methyl.
3. A method according to claim 1 or 2 in which the copolymer is derived from acrylic acid, methacrylic acid or maleic acid.
4. A method according to any one of claims 1 to 3 in which Y represents
Figure imgb0018
5. A method according to any one of claims 1 to 4 in which the molar ratio of the units of formula (II) to units of formula (III) or (IV) is from 1:4 to 4:1.
6. A method according to any one of the preceding claims in which the polyampholyte is also derived from acrylamide or a C₁-C₄ alkyl or hydroxyalkyl acrylate or methacrylate.
7. A method according to any one of the preceding claims in which the phosphonate is added to the system in an amount from 1 to 100 ppm.
8. A method according to claim 7 in which the phosphonate is added in an amount from 10 to 30 ppm.
9. A method according to any one of the preceding claims in which the polyampholyte is added in an amount from 0.1 to 150 ppm.
10. A method according to claim 9 in which the polyampholyte is added in an amount from 1 to 40 ppm.
11. A method according to any one of the preceding claims in which the aqueous system is a cooling water system.
EP90303075A 1984-11-08 1990-03-22 The inhibition of corrosion in aqueous systems Withdrawn EP0396243A1 (en)

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Application Number Priority Date Filing Date Title
GB08428258A GB2168359B (en) 1984-11-08 1984-11-08 A method of inhibiting corrosion in aqueous systems
GB8910051 1989-05-03
GB8910051A GB2231565B (en) 1984-11-08 1989-05-03 The inhibition of corrosion in aqueous systems

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EP90303075A Withdrawn EP0396243A1 (en) 1984-11-08 1990-03-22 The inhibition of corrosion in aqueous systems

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EP (2) EP0181151B1 (en)
JP (1) JPS61119689A (en)
AU (1) AU572355B2 (en)
CA (2) CA1268029A (en)
DE (1) DE3586086D1 (en)
ES (1) ES8606875A1 (en)
GB (2) GB2168359B (en)
PH (1) PH21891A (en)
SG (1) SG51688G (en)
ZA (2) ZA858294B (en)

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ES8606875A1 (en) 1986-05-16
EP0181151A1 (en) 1986-05-14
CA1268029A (en) 1990-04-24
GB2231565A (en) 1990-11-21
AU4911485A (en) 1986-05-15
US4692317A (en) 1987-09-08
ZA858294B (en) 1986-06-25
CA2015718A1 (en) 1990-11-03
GB2168359B (en) 1988-05-05
SG51688G (en) 1989-05-26
ZA903288B (en) 1991-02-27
JPH0526875B2 (en) 1993-04-19
PH21891A (en) 1988-03-25
GB8428258D0 (en) 1984-12-19
GB2168359A (en) 1986-06-18
JPS61119689A (en) 1986-06-06
EP0181151B1 (en) 1992-05-20
ES548611A0 (en) 1986-05-16
AU572355B2 (en) 1988-05-05
GB8910051D0 (en) 1989-06-21
DE3586086D1 (en) 1992-06-25
GB2231565B (en) 1992-08-26

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